75835-25-5Relevant academic research and scientific papers
Palladium-Catalyzed Hiyama Coupling of Benzylic Ammonium Salts via C-N Bond Cleavage
Han, Chunyu,Zhang, Zhenming,Xu, Silin,Wang, Kai,Chen, Kaiting,Zhao, Junfeng
, p. 16308 - 16313 (2019/12/25)
The first palladium-catalyzed Hiyama cross-coupling of arylsilanes with benzyltrimethylammonium salts is reported. The reaction proceeds smoothly to facilitate C(sp2)-C(sp3) bond formation via cleavage of the C-N bond and provides a useful approach to various diarylmethanes with a broad substrate scope and excellent functional group tolerance in good to excellent yields.
Visible-light-mediated external-reductant-free reductive cross coupling of benzylammonium salts with (hetero)aryl nitriles
Miao, Meng,Liao, Li-Li,Cao, Guang-Mei,Zhou, Wen-Jun,Yu, Da-Gang
, p. 1519 - 1524 (2019/11/03)
Herein we report a novel visible-light-mediated external reductant-free reductive cross coupling for the construction of C sp2–C sp3 bonds. A variety of benzylammonium salts underwent selective coupling with (hetero)aryl nitriles to
A SO2F2 mediated mild, practical, and gram-scale dehydroxylative transforming primary alcohols to quaternary ammonium salts
Zhao, Chuang,Zha, Gao-Feng,Fang, Wan-Yin,Alharbi, Njud S.,Qin, Hua-Li
, p. 4648 - 4656 (2019/07/12)
A simple, practical and gram-scale process for direct transformation of primary alcohols or silyl ethers to ammonium salts was developed. This method has the feathers of easy work-up (a simple filtration), mild condition, high yield, great practicality and robustness. And the application of the ammonium salts in Suzuki coupling reaction was also accomplished.
Palladium catalyzed Suzuki cross-coupling of benzyltrimethylammonium salts via C-N bond cleavage
Wang, Tao,Yang, Shuwu,Xu, Silin,Han, Chunyu,Guo, Ge,Zhao, Junfeng
, p. 15805 - 15808 (2017/03/22)
A palladium catalyzed Suzuki cross-coupling for construction of Csp3-Csp2 bond via Csp3-N bond activation of benzyltrimethyl-ammonium salt is described. This reaction not only offered a highly efficient approach to diarylmethanes but also paved the way for the application of benzyltrimethylammonium salts in the palladium catalyzed cross coupling reactions.
Iridium-Catalyzed Borylation of Primary Benzylic C-H Bonds without a Directing Group: Scope, Mechanism, and Origins of Selectivity
Larsen, Matthew A.,Wilson, Conner V.,Hartwig, John F.
supporting information, p. 8633 - 8643 (2015/07/15)
Primary benzylic boronate esters are useful intermediates in organic synthesis, but these reagents cannot be prepared by hydroboration. The benzylic C-H borylation of methylarenes would be a method to form these products, but such reactions without neat methylarene or a directing group are unknown. We report an approach to divert the borylation of methylarenes from aromatic positions to benzylic positions with a silylborane as reagent and a new iridium catalyst containing an electron-deficient phenanthroline as ligand. This system forms benzylic boronate esters selectively over the corresponding aryl boronate esters. An Ir diboryl monosilyl complex ligated by the phenanthroline was isolated and determined to be the resting state of the catalyst. Mechanistic studies show that this complex is kinetically competent to be an intermediate in the catalytic process. Kinetic studies of benzylic and aryl C-H borylation catalyzed by various Ir complexes show that the rate of aryl C-H borylation decreases with decreasing electron density at the metal center of the Ir catalyst, but that the rate of benzylic C-H borylation is less sensitive to the degree of electron density at the metal center of the Ir catalyst. Kinetic and computational studies suggest that the two borylation reactions respond differently to the degree of electron density at the metal center because they occur with different turnover-limiting steps. The turnover-limiting step in the borylation of aryl C-H bonds is known to be C-H oxidative addition, but the turnover-limiting step of the borylation of benzylic C-H bonds appears to be an isomerization prior to C-B reductive elimination.
Single-electron transmetalation in organoboron cross-coupling by photoredox/nickel dual catalysis
Tellis, John C.,Primer, David N.,Molander, Gary A.
, p. 433 - 436 (2014/08/05)
The routine application of Csp3-hybridized nucleophiles in cross-coupling reactions remains an unsolved challenge in organic chemistry. The sluggish transmetalation rates observed for the preferred organoboron reagents in such transformations are a consequence of the two-electron mechanism underlying the standard catalytic approach. We describe a mechanistically distinct single-electron transfer-based strategy for the activation of organoboron reagents toward transmetalation that exhibits complementary reactivity patterns. Application of an iridium photoredox catalyst in tandem with a nickel catalyst effects the cross-coupling of potassium alkoxyalkyl- and benzyltrifluoroborates with an array of aryl bromides under exceptionally mild conditions (visible light, ambient temperature, no strong base). The transformation has been extended to the asymmetric and stereoconvergent cross-coupling of a secondary benzyltrifluoroborate.
Electroorganic reactions. Part 56: Anodic oxidation of 2-methyl- and 2-benzylnaphthalenes: Factors influencing competing pathways
Utley, James H.P,Rozenberg, Gregor G
, p. 5251 - 5265 (2007/10/03)
A systematic investigation of the anodic oxidation in nucleophilic media of 2-methyl and 2-benzylnaphthalenes, substituted at the 6-position in the naphthalene nucleus and at the 4-phenyl position of the benzylic side chain, has been carried out to identify factors favouring side-chain substitution. Cyclic voltammetry confirms that 6-substitution has a profound effect on the oxidation potentials of the naphthalene nucleus and 13C chemical shifts indicate polar effects at the benzylic carbon. However, little side-chain anodic oxidation is observed under any conditions tried; the radical-cations of electron-rich substrates preferentially dimerise and a strongly electron-withdrawing substituent at the 6-position (EtOSO2) promotes nuclear substitution. In contrast, oxidation with DDQ in aqueous acetic acid gives efficient side-chain oxidation for electron rich substrates, consistent with hydride transfer, possibly intramolecularly via a charge transfer complex.
AROMATIZATION OF ALIPHATIC COMPOUNDS - V. m-DIALKIYL-BENZENES AND 2-BENZYL-NAPHTALENES
Giannangeli, M.,Baiocchi, L.
, p. 1381 - 1384 (2007/10/02)
Same cyclohexadienols, when heated at 220 deg C with PyHCl, gave, through dehydration and isomerisation, the corresponding benzene derivatives.So 2,6-dibenzyliden-cyclohexanols gave m-dibenzyl-benzenes, 2-benzyliden-1-tetralols gave 2-benzyl-naphtalenes a
